JP2014167113A - Method of producing composite material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite material which has expansibility and a high ion conductivity, especially proton conductivity, even when the operation temperature of an electrochemical cell is set to be higher than 100°C and is used in e.g. membrane fuel cells.SOLUTION: A method of producing a composite material composed of an ionomer and laminar or network functionalized silicates. The ionomer is a polymer consisting of (a) a cation exchange polymer, (b) an anion exchange polymer, (c) a polymer having both cation exchange groups and anion exchange groups in polymer chains or (d) a mixture of (a) and (b) in a mixing ratio of 100% (a) and 100% (b), with the mixture crosslinked ionically and optionally covalently.

Description

  Ionomer membranes are used in many processes such as membrane fuel cells, electrodialysis, diffusion dialysis, electrolysis (PEM electrolysis, chlor-alkali electrolysis) or electrochemical processes. However, commercially available membranes have the disadvantage that proton conductivity is drastically reduced because the membranes are almost always dried in the temperature range higher than 100 ° C. However, at temperatures higher than 100 ° C., the temperature control of the fuel cell becomes very simple and the catalyst of the fuel cell reaction is essentially improved (it can be harmful to the catalyst, the overvoltage is reduced and there is no CO adhesion) Therefore, the temperature range higher than 100 ° C. is very interesting for a fuel cell using an ionomer membrane.

  Only a few examples of membranes exhibiting good proton conductivity at temperatures above 100 ° C., such as polyphenylene with carbonyl-1,4-phenyleneoxyphenyl-4-sulfonic acid end groups, are known from the literature. However, the proton conductivity of these membranes also drops rapidly at temperatures higher than 130 ° C., and the reason for good proton conductivity between 100 ° C. and 130 ° C. is unknown.

Based on the Grotthus mechanism, proton conduction appears as protons in acidic solvents and as protons in hydroxide ions in alkaline solutions. In fact, hydrogen bonds that allow charge transport exist as a cross-linked structure. That is, the water present in the membrane plays a role of assisting the charge transfer. Without this auxiliary water in these commercially available membranes, little charge transfer through the membrane occurs and its function is lost. Other newly developed methods that work with phosphate backbones instead of fluorinated hydrocarbon backbones also require water as an auxiliary cross-linker (Alterti et al., SSPC9, Bredo, Slovenia, August 1998). 17-21 days, extended abstracts, p. 235). By adding fine SiO ₂ particles to the og membrane (Antonucci et al., SSPC9, Bled, Slovenia, Aug. 17-21, 1998, Extended Abstracts, page 187), proton conduction is stabilized to 140 ° C. But only under operating pressure conditions of 4.5 bar. If the operating pressure is not increased, again these membranes lose water crosslinks at temperatures above 100 ° C. and dry. The essential disadvantage of all og membrane types is that they are only suitable for use at temperatures up to 100 ° C. even under optimal operating conditions.

  Similar to the method described above, Denton et al. (US Pat. No. 6,042,958) made a composite of ion conducting polymer and a multi-porous substrate. Glass, ceramic material or silica was used as the silicic acid component. In the disclosed examples, the operating temperature again did not exceed 80 ° C.

  In direct methanol fuel cells, water is in fact sufficient, but flowing methanol through the membrane leads to a significant loss of capacity.

  A new composite of sulfonated polyaryletheretherketone membrane (European Patent No. 0574791B1) or sulfonated polyethersulfone membrane and silica has been made, but with a cation exchange capacity of 1.5 (meq / g) It flows through the membrane and is too strong, so the membrane is eventually destroyed.

  The advantages of the composites and membranes made therefrom suitable for this invention are that, when a protonated nitrogen base is present in one of the polymer backbones, it stores organic components, in particular protonation that is representative of cross-linking components. Nitrogen base is stored in the pores of the layered silicate. Furthermore, the intentional storage of cations or metal hydroxides, followed by corresponding metal oxide conversion, can vary the properties of the Lewis acid and the size of the pores of the membrane extensively. The layered silicate can be further functionalized to either interact with the incorporated ionomer or affect the surrounding medium according to the functional group.

Layered silicates (clay minerals) have interesting properties.
・ Hydrogen water is retained up to 250 ℃.
It is also possible to store metal cations and metal oxides in these substances, thereby causing internal proton conductivity as in the following general system:
M ^{n +} (H ₂ O)-> (M-OH) ^{(n-1) +} + H ⁺ [Zeolite, clay and hereropoly acid in organic reactions, Y. Izumi, K. Urabe, M.M. Onaka, 1992, Weinheim, VCH Publishing, page 26].
・ Layered silicates showing Lewis acid vacancies can be intercalated by base groups and acid-base interactions of base polymers [Plastic nanocomposites, Symposium: From invention to innovation, 1998 Publication for the Symposium on Chemical Industry Fund in Cologne, May 6 (Kunststoffnanokomposite, Symposium: Von der Invention zur Innovation, Publikationzum Symposium des Fonds der Chemishen Industrieam 6. Mai 1998 in Koln)]. Due to this property, certain layered silicate / polymer composites have already been synthesized. Therefore, Muhlhaupt et al. Make composites of montmorillonite and polypropylene, montmorillonite and polyamide, and montmorillonite and plexiglass. With these composites, for example, plexiglass becomes nonflammable by a mixture with montmorillonite. This is because the mixed layered silicate serves as a barrier against the pyrolysis gas generated by combustion.

  With such a technical situation as a starting point, the object of the present invention is to provide ionic conductivity (particularly proton conductivity) even when the operation temperature of the electrochemical cell is higher than 100 ° C. It is to provide a high complex. Accordingly, an object of the present invention is an ion-conducting complex having an acid and / or organic base and a layered silicate, the composition of which is an acid-base ratio of 1 to 99% by weight, and the layered silicate Is 99 to 1% by weight.

It is a figure for demonstrating an example of the composite_body | complex and composite film of this invention.

(A) a cation exchange polymer (having a cation exchange group —SO ₃ H, —COOH, —PO ₃ H ₂ ), and the polymer is either one of the cation exchange groups or the cation exchange groups; It can be modified only with a mixture). In this case, the polymer may not form a crosslink or may form a crosslink covalently. In general, the ion exchange capacity is preferably 0.1 to 12 meq / g. In particular, 0.3 to 8 meq / g is preferable. Furthermore, 0.5 to 2 meq / g is preferable. Here, a thermoplastic resin is particularly suitable as the skeleton chain.

(B) The acid may be an organic or inorganic low molecular acid. As the inorganic acid, sulfuric acid and phosphoric acid are particularly preferable. As the organic acid, all low-molecular acids of sulfonic acid or carboxylic acid, particularly aminosulfonic acid and aminosulfochloride as a precursor thereof can be used.

(C) a base as an anion exchange polymer (anion exchange group —NR ₃ ⁺ (R═H, alkyl, aryl), pyridinium PyrR ⁺ , imidazolium ImR ⁺ , pyrazolium PyrazR ⁺ , triazolium TriR ⁺ and other organic base aromas And / or non-aromatic (R = H, alkyl, aryl), and the polymer can be modified with any of the anion exchange groups or a mixture of the anion exchange groups alone. . In this case, the polymer may not form a crosslink or may form a crosslink covalently. In this case, the anion exchange capacity is generally preferably 1 to 15 meq / g. In particular, 3 to 12 meq / g is preferable, and 6 to 10 meq / g is more preferable. In this case as well, all thermoplastic resins, particularly polysulfone, polyetheretherketone, polybenzimidazole and polyvinylpyridine are preferred as the skeleton chain.

(D) The base can be an organic or inorganic low molecular weight base. As the organic low molecular base, all guanidine derivatives are particularly preferable.

(E) Acid and base functional groups can be present in the same molecule. These molecules can be small molecules or polymers. If it is a polymer, both the anion exchange group of (c) and the cation exchange group of (a) are present on the polymer chain.

(F) The acid and base of (a) to (e) can be mixed in the complex. In this case, any mixing ratio can be applied. In this case, this mixing can form a crosslink covalently in addition to the ionic crosslink.

(G) Since both acids and bases are small molecules, unmodified polymers are further included in the complex.

(H) Inorganic active fillers are montmorillonite, smectite, illite, sepiolite, palygorskite, mascobite, allefardite, amesite, hectorite, talc, fluorinated hectorite, saponite, beidellite, nontronite, stevensite. , Bentonite, mica, vermiculite, vermiculite fluoride, halloysite, layered silicate based on fluorine-containing synthetic talcum powder, or a mixture of two or more of the above layered silicates. The layered silicate can be delaminiert or pillared. Montmorillonite is particularly preferable. The weight ratio of the layered silicate can be 1 to 80%, preferably 2 to 30% by weight and in particular 5 to 20% by weight.

(Description of functionalized layered silicate)
Below the layered silicate is a common silicate in which the SiO ₄ tetrahedra are connected by two-dimensional infinite cross-linking. (The empirical formula for anions is (Si ₂ O ₅ ²⁻ ) _n .) The individual layers are bonded to one another by cations in between. In that case, most of the cations in the naturally occurring layered silicate are Na, K, Mg, Al and / or Ca.

Underneath the delaminated functionalized layered silicates, layered silicates can be seen in which the distance between adjacent layers is increased by conversion with a so-called functionalizing agent (Funktionalisierungsmitteln). The layer thickness of the delaminated silicate is usually 5 to 100 angstroms, preferably 5 to 50 angstroms and in particular 8 to 20 angstroms. In order to increase the interlaminar distance (hydrophobize), the layered silicate is converted with a so-called functional hydrophobizing agent (before making the composite suitable for the present invention). This is often called an onium ion or onium salt.
Depending on the type of each functionalized molecule or polymer that directly incorporates the layered silicate, the layered silicate cation is converted with an organic functionalized hydrophobizing agent, depending on the type of organic residue desired A distance can be obtained. The exchange of metal ions can occur completely or partially. Preferably, the exchange of metal ions is complete. The amount of exchangeable metal ions is usually expressed in milliequivalents (meq) per 1 g of layered silicate, and this is called the ion exchange capacity. The cation exchange capacity of the layered silicate is preferably at least 0.5, more preferably 0.8 to 1.3 meq / g.

Suitable organofunctional hydrophobizing agents are derived from oxonium, ammonium, phosphonium and sulfonium ions having one or more organic residues. Suitable functional hydrophobizing agents include general formulas I and / or II.
Here, the substituent has the following characteristics.
R 1, R 2, R 3, R 4 are different hydrogens or linear, branched, saturated or unsaturated hydrocarbons having 1 to 40, preferably 1 to 20 carbon atoms, optionally at least In heterocyclic residues having one functional group or two residues bonded to each other, preferably having 5 to 10 carbon atoms, in particular having one or more nitrogen atoms X is phosphorus or nitrogen, Y is oxygen or sulfur, n is an integer from 1 to 5, preferably 1 to 3, and Z is one anion.
Suitable functional groups are hydroxyl, nitro or sulfo groups, where carboxyl and sulfonic acid groups are particularly preferred. Likewise, sulfochlorides and carboxylic acid chlorides are particularly preferred.

  Preferred anions Z are proton supplying acids, especially inorganic acids, halogens such as chlorine, bromine, fluorine, iodine, sulfates, sulfonates, phosphates, phosphonates, phosphites and carboxylates, especially acetates. . The layered silicate used as a substrate is usually converted into a suspension state. A preferred suspending agent is water, optionally a mixture with an alcohol, in particular with a lower alcohol having 1 to 3 carbon molecules. Since the functional hydrophobizing agent is insoluble in water, a solvent that dissolves it is preferred. In particular, it is an aprotic solvent. Further examples of suspending agents are ketones and hydrocarbons. Usually, a water miscible suspension is preferred. A hydrophobizing agent is added to the layered silicate to cause ion exchange, thereby preventing sedimentation of the layered silicate. The metal salt produced as a by-product of ion exchange is preferably water-soluble, so that the hydrophobic layered silicate as a crystalline solid material can be separated, for example, by filtration. Ion exchange is largely independent of reaction temperature. This temperature is preferably higher than the crystallization temperature of the medium and lower than the boiling point. Since it is aqueous, this temperature is 0 to 100 ° C., preferably 40 to 80 ° C.

  For cation and anion exchange polymers, alkylammonium ions are preferred, especially when the carboxylic acid chloride or sulfonic acid chloride is further present as a functional group in the same molecule. Alkyl ammonium ions are general methylating agents such as commercially available methyl iodide. The preferred ammonium ions are omega-amino carboxylic acids, especially omega-amino sulfonic acids and omega-alkyl amino sulfonic acids. Omega-amino sulfonic acids and omega-alkyl amino sulfonic acids can be obtained with common inorganic acids such as hydrochloric acid, sulfuric acid or phosphoric acid, or from methylating agents such as methyl iodide. More preferred ammonium ions are pyridine and lauryl ammonium ions. After hydrophobization, the layered silicate usually has an interlayer distance of 10 to 50 angstroms, preferably 13 to 40 angstroms.

  The hydrophobized and functionalized layered silicate is dried to eliminate water. Usually, the layered silicates thus treated still contain water with a residual moisture content of 0 to 5% by weight. The hydrophobized layered silicate can then be mixed with the polymer and further processed as a suspension of maximally dry suspension. This polymer is suitable for the present invention, and a thermoplastic functionalized polymer (ionomer) suitable for a suspension of hydrophobized layered silicic acid is obtained. This can be in dissolved form or the polymer can be placed in the suspended material itself in solution. Usually, the proportion of layered silicate is 1 to 70% by weight. It is preferably 2 to 40%, particularly 5 to 15% by weight.

(Production method of composite)
The invention further relates to a method for producing a composite membrane. An example of production of a proton conductive compound having high proton conductivity will be described below.

1) Dissolve aminoarylsulfochloride in tetrahydrofuran. Thereafter, a corresponding amount of montmorillonite K10 is added. Montmorillonite is proton exchanged and dried. Then, it is stirred for several hours. The stirring time depends on the molecular size of aminoarylsulfochloride and the ratio of amino groups to the cation exchange capacity of montmorillonite. During the stirring process, amino groups are intercalated into montmorillonite vacancies. Here, the sulfochlorinated polysulfone is dissolved in tetrahydrofuran as a suspension. The amount of sulfochloride in the thermoplastic resin is about 0.5 groups per repeating unit. The suspension is stirred and carefully degassed to form a film on the glass plate. Tetrahydrofuran (THF) is evaporated at room temperature. The amount of montmorillonite is selected so that the added sulfochlorinated polysulfone is 5 to 10% by weight. The film is completely dried, peeled off in demineralized water and then post-treated at 90 ° C. in 10% hydrochloric acid.

At this time, the sulfochloride group is hydrolyzed and converted into a sulfonic acid group. The resulting membrane is further post-treated with hot water at 80-90 ° C. so that hydrochloric acid is no longer detected. A sulfochlorinated polysulfone having 0.5 SO ₂ Cl per repeating unit corresponds to a cation exchange capacity of 1.0 meq / gram after hydrolysis. The added sulfonic acid group from the aminoarylsulfochloride significantly increases the cation exchange capacity depending on the amount and makes it water-insoluble. At the same cation exchange capacity, it is water soluble except for the sulfonated polysulfone.

2) Dissolve the sulfonated polyetheretherketone having a cation exchange capacity (IEC) of 0.9 meq / gram in N-methylpyrotidone (NMP) at high temperature (T> 80 ° C.). The sulfochlorinated form of this component is insoluble in THF. The polymeric sulfonic acid and its salts are completely or almost insoluble in THF. Here, an NMP suspension of montmorillonite K10 loaded with aminosulfonic acid is added to this solution. The sulfonic acid group is near the surface, while the amino group is in the pores of montmorillonite. The suspension combination is again selected so that the solids are between 2 and 20% by weight of the polymer amount. This depends on the range of use in which the membrane is required. The membrane is dried in an oven at a temperature of 80 to 150 ° C. The membrane is peeled from the glass plate and post-treated at 90 ° C. for 12 hours in demineralized water.

3) Dissolve sulfochlorinated polysulfone and aminated polysulfone in THF. 10% by weight of montmorillonite K10 (dried and protonated form) is then added. The suspension is stirred and degassed to obtain the membrane. After peeling from the glass plate, the membrane is post-treated at 80 ° C. in dilute hydrochloric acid. Again, the sulfochloride group is hydrolyzed to sulfonic acid. The membrane is then further treated with demineralized water to completely remove hydrochloric acid from the membrane.

The following surprising properties of the composite according to the invention have been found:
The composite exhibits very high ionic conductivity at temperatures much higher than 100 ° C. In particular, even in this temperature range, the proton conductivity of the composite is very good. This is due to the water retention properties of the clay mineral on the one hand and to the intrinsic proton conductivity of the clay mineral on the other hand. Due to the good proton conductivity, this composite can be applied to the fuel cell membrane in the above temperature range.
・ Polymer molecules such as zeolite and clay minerals can interact with each other in the pores, so the chemical, mechanical and thermal stability of the composite membrane is significantly improved by providing pores in the silicate. . In particular, it is possible to intercalate the basic polymer and basic polymer component containing the ionomer mixture by the interaction of basic groups in the Lewis acid vacancies of the silicate. This forms an ionic bridge between the acid silicate and the basic polymer chain, which does not depend on the pH of the system, especially when the composite membrane is placed in a strong acid or base medium. Contributes to improving chemical and thermal stability.

-When applied to DMFC, the composite membrane suitable for the present invention has reduced methanol permeability and gas diffusibility to the membrane. At this time, methanol permeability and selective permeability of the membrane can be intentionally adjusted as follows.
Layered- / reticulated silicate type.
The weight percentage of silicate in the complex.
Intentional introduction of spacer molecules and bifunctional molecules into silicate vacancies. At this time, the type and strength of the interaction between the spacer molecule and the permeable molecule are determined by the type of the functional group exposed in the membrane and the type of the functional group of the permeable molecule. In exchange for alkali bentonite on the bentonite surface, for example, amino sulfonic acid or amino carboxylic acid and an amine function (Aminfunktion) are combined. The second functional group can be used in a reaction with a polymer or a proton transfer electromembrane method.

The membrane suitable for the present invention has very little deposits (microbial corrosion of the ionomer membrane by fungi and bacteria) compared to the conventional ionomer membrane, and 2 to 5 of silicate (montmorillonite) in the ionomer membrane. % By weight. This is caused by clay minerals mixed in the composite. It has already been known for many years that clay minerals act as soil conditioners by delaying microbial degradation, in particular by fungi. Surprisingly, this property of clay minerals also works for clay mineral-containing films. This property of the composite suitable for the present invention allows it to be applied to membrane separation techniques in the water treatment and wastewater treatment field and to any oxidizing environment, for example an environment containing hydroxy radicals and / or hydrogen peroxide.
The catalytic properties of the silica compound Lewis acid that constitutes the clay mineral suitable for the present invention can also be used in the composite suitable for the present invention.

(Example)
1. Sulfonated polyetheretherketone (sulfonation rate 70%) is dissolved in 5% by weight of montmorillonite and DMAc, and the solvent is evaporated to obtain a film having a thickness of 50 μm. The membrane is placed in an aqueous medium contaminated with fungi. Degradation by fungi is not detected. In the control without montmorillonite, breeding occurs and is degraded.

2. a) The sulfonated polysulfone in salt form and polyvinylpyridine are mixed in a ratio such that a final mixture of 1 milliequivalent [H +] / g total mixture is obtained. Both polymers are dissolved in DMAc to obtain a membrane. The specific resistance of the obtained film is 33 [Ω × cm].
b) 2. 1. Add 8% by weight of activated montmorillonite to the same mixture as a. A film is obtained in the same manner as a. The specific resistance is 27.7 [Ω × cm].

3. Polybenzimidazole dissolved in DMAc is mixed with 10% by weight of activated montmorillonite, and the one without layered silicate is used as a control. Membranes are made from both mixtures and the resistance is measured by impedance spectroscopy. Those without layered silicate have a resistance value of 588 [Ω × cm], and those with layered silicate have 276 [Ω × cm].
<1>
Proton conductive composite containing an acid and / or organic base and a layered / reticulated silicate, wherein the proportion of the acid-base complex is 1 to 99% by weight, and the proportion of the layered / reticulated silicate Is 99 to 1% by weight.
<2>
A method for producing a composite and composite mixed film, comprising mixing an ionomer solution or a solution of an ionomer precursor with a layered or reticulated silicate, or a mixture of both, and evaporating the solvent from the resulting suspension. A method characterized by. Here, the ionomer includes (a) a cation exchange polymer (having a cation exchange group —SO ₃ H, —COOH, —PO ₃ H ₂ , and the polymer is added to any one of the cation exchange groups or the cation exchange group. Those that can be modified only with a mixture of ion exchange groups). Here, the polymer does not form crosslinks or can form crosslinks covalently. Here, the polymer backbone can be a vinyl polymer, an aryl main chain polymer, polythiazole, polypyrazole, polypyrrole, polyaniline, polythiophene or any mixture thereof.
(B) anion exchange polymers (anion exchange groups —NR ₃ ⁺ (R═H, alkyl, aryl), pyridinium PyrR ⁺ , imidazolium ImR ⁺ , pyrazolium PyrazR ⁺ , triazolium TriR ⁺ and other organic base fragrances and / or Or a non-aromatic group (R = H, alkyl, aryl), and the polymer can be modified only with any of the anion exchange groups or a mixture of the anion exchange groups). Here, the polymer does not form crosslinks or can form crosslinks covalently. Here, the polymer backbone can be a vinyl polymer, an aryl main chain polymer, polythiazole, polypyrazole, polypyrrole, polyaniline, polythiophene or any mixture thereof.
(C) A polymer having both the anion exchange group of (a) and the cation exchange group of (b) on the polymer chain. Here, the polymer backbone can be a vinyl polymer, an aryl main chain polymer, polythiazole, polypyrazole, polypyrrole, polyaniline, polythiophene or any mixture thereof.
(D) A mixture of (a) and (b), wherein the mixing ratio can reach from (a) 100% to (b) 100%. Here, in addition to the ionic crosslinking, the mixture further forms a covalent crosslinking. Here, the polymer backbone can be a vinyl polymer, an aryl main chain polymer, polythiazole, polypyrazole, polypyrrole, polyaniline, polythiophene or any mixture thereof.
Here, as an ionomer precursor, (a) a precursor of a cation exchange resin.
(A1) CoHal-, CONR ₂ - or COOR- group (R = H, alkyl, aryl, Hal = F, Cl, Br , I) a polymer having a.
(A2) A polymer having SO ₂ Hal—, SO ₂ NR ₂ — or SO ₂ OR— groups (R = H, alkyl, aryl, Hal = F, Cl, Br, I).
(A3) A polymer having PO ₃ Hal ₂ —, PO ₃ (NR ₂ ) ₂ — or PO ₃ (OR) ₂ — groups (R = H, alkyl, aryl, Hal = F, Cl, Br, I) .
(B) a precursor of an anion exchange resin (NR ₂ - group (R = H, alkyl, aryl), pyridyl Pyr, imidazolyl Im, pyrazolyl Pyraz, triazolyl Tri and / or other organic bases aromatic and / or nonaromatic groups Have). Here, the inorganic component can be a layered silicate or a reticulated silicate or any mixture thereof.
<3>
a) The method according to <2>, wherein among the layered silicate (phyllosilicate) group, a bentonite group, particularly a montmorillonite / biderite system, and further montmorillonite are suitable.
b) The method according to <2>, wherein a pillared layered silicate is used.
<4>
a) The method according to the item <2>, wherein the group of reticulated silicates (tectosilicates) is generally preferably a zeolite group, particularly clinoptilolite.
b) The method according to <2>, wherein a pillared reticulated silicate is used.
<5>
The method according to any one of <2> to <4>, wherein both a natural layered silicate and a synthetic layered silicate are used.
<6>
Base component is imidazole, vinylimidazole, pyrazole, oxazole, carbazole, indole, isoindole, dehydrooxazole, isoxazole, thiazole, benzothiazole, isothiazole, benzimidazole, imidazolidine, indazole, 4,5-dihydropyrazole, 1, 2,3-oxadiazol, furazane, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,3-benzotriazole, 1,2,4-triazole, tetrazole, pyrrole, aniline, pyrrolidine Or it has a pyrazole group, The method of said <2> characterized by the above-mentioned.
<7>
The process according to <2>, wherein the acid-base mixture (d) as an ionomer and the clay mineral montmorillonite of both synthetic and natural origin are suitable and functionalized.
<8>
The method according to <2>, wherein the acid-base mixture (d) is suitable as the ionomer and clinoptilolite is suitable as the zeolite.
<9>
The method according to any one of <2> to <8>, wherein the polymer backbone of the acid polymer is selected from the aryl main chain polymer group. A possible structure of the aryl main chain polymer is as follows.
From the structure of the above formula, possible synthetic aryl main chain polymers are: -polyetheretherketone PEEK Victrex® ([R ₅ -R ₂ -R ₅ -R ₂ -R ₇ ] n; x = 1, R ₄ = H)
- polyethersulfone PSU Udel (registered _{trademark) ([R 1 -R 5 -R} 2 -R 6 -R 2 -R 5] n; R 2: x = 1, R 4 = H)
- polyethersulfone PES VICTREX _{(TM) ([R 2 -R 6 -R} 2 -R 5] n; R 2: x = 1, R 4 = H)
- polyphenylsulfone RADEL R _{(TM) ([(R 2) 2} -R 5 -R 2 -R 6 -R 2] n; R 2: x = 2, R 4 = H)
- polyetherethersulfone RADEL A _{(TM) ([R 5 -R 2 -R} 5 -R 2 -R 6] n- [R 5 -R 2 -R 6 -R 2] m; R 2: x = 1, R ₄ = H, n / m = 0.18)
- polyphenylene sulfide _{PPS ([R 2 -R 8]} n; R 2: x = 1, R 4 = H) - poly ferri alkylene oxide _{PPO ([R 2 -R 5]} n; R 4 = CH 3)
It is.
<10>
The method according to <2> above, wherein the polymer backbone of the base polymer is selected from an aryl main chain polymer group [Chemical Formula 2] or a hetaryl main chain polymer. A possible structure of the hetaryl main chain polymer is as follows.
The structure of the polymer in the formula is 1 imidazole, 2 benzimidazole, 3 pyrazole, 4 benzpyrazole, 5 oxazole, 6 benzoxazole, 7 thiazole, 8 benzthiazole, 9 triazole, 10 benztriazole, 11 pyridine, 12 bipyridyl, 13 Phthalimide.
As the hetaryl polymer suitable for the present invention, the following may be considered.
-Polyimidazole, polybenzimidazole-polypyrazole, polybenzpyrazole- polyoxazole, polybenzoxazole-polythiazole, polybenzthiazole-polythiophene, polybenzthiophene-polypyridine-polyimide <11>
In the acid-base mixture, the acid polymer described in <9> [Chemical Formula 2] is combined with the base polymer described in <10> [Chemical Formula 3] and <6> above, <2> to <10>.
<12>
Nonionic conductive composite and composite mixed film, wherein in <1> to <11>, 20 to 98% by weight of the base polymer and 2 to 80% by weight of the layered / network silicate are used for the film and the film Nonionic conductive composites and composite mixed membranes that can be obtained by use in separation methods.
<13>
Incorporated in -40 ℃ to membrane fuel cell at a temperature of 200 ° C. (H ₂ fuel cells or direct methanol fuel cell), complexes and complex mixed film according to any one of the <1> to <11> .
<14>
It is characterized by incorporating composites and composite mixed membranes into (electric) membrane separation methods such as dialysis, diffusion dialysis, gas separation, pervaporation, osmotic extraction, microfiltration, ultrafiltration, nanofiltration and reverse osmosis. The method according to any one of <2> to <12>.
<15>
<1> thru | or <12> any one of <1> thru | or <12> characterized by including as a catalyst membrane or a membrane reaction apparatus.
<16>
The complex according to any one of <1> to <12>, for covering a planar structure, particularly a film, a foil, and an electrode.
<17>
The composite according to the above <2>, wherein the organic component and the silicate component suitable for the present invention are brought into contact with each other at a temperature of −40 ° C. to 300 ° C. in a solvent or optionally without a solvent. Body manufacturing method.
<18>
The composite containing the proton conductor according to any one of <1> to <17>, which has temperature stability up to 400 ° C.
<19>
<2>, <6>, <9>, <10> and a corresponding mixture or a single component according to <11>, which is present together with a silicate component which is solution or suspension or solvent free The production of the composite membrane or composite according to <16>, wherein the membrane is coated with a mixture or a component to be produced.
<20>
It is coated with the solution or suspension of claim <2>, <6>, <9>, <10> and <11> or the silicate component itself or a mixture of components which is solvent-free. Production of the composite membrane or composite according to <16>.
<21>
Built into membranes and (electrical) membrane separation methods such as dialysis, diffusion dialysis, gas separation, pervaporation, osmotic extraction, microfiltration, ultrafiltration, nanofiltration and reverse osmosis, and stable against microbial degradation or oxidative corrosion Manufacture of composites characterized by being.
<22>
The production of a complex according to any one of <1> to <21>, wherein the permselectivity of a membrane produced from the complex is changed.
<23>
The production of the complex according to any one of <1> to <22>, wherein the inorganic component is mixed with at least two different base components. Here, the base component can be a polymer or a low molecule.
<24>
Incorporating the complex into any mold that shares the mold.

Claims (2)

A method for producing a composite, comprising: preparing the following components (A) to (D); and bringing the components (A) to (D) into contact with each other at a temperature of −40 ° C. to 300 ° C. A method comprising the steps of:
Method.
A composite comprising (A) a polymer, (B) an acid, (C) an organic base, and (D) a functionalized layered or networked silicate, the sum of the acid, base, and the layered or networked silicate Based on the amount, the proportion of the acid and base mixture is 1 to 99% by weight, the proportion of the layered or reticulated silicate is 99 to 1% by weight,
The complex is
i) further comprising (E) an unmodified polymer and a low molecular acid and base, or
ii) (F) an ionomer or ionomer precursor, comprising:
The ionomer is
(A) It has a cation exchange group —SO ₃ H, —COOH and / or —PO ₃ H ₂ , does not form a crosslink or forms a crosslink covalently, and the polymer backbone is vinyl A cation exchange polymer that is a polymer, aryl backbone polymer, polythiazole, polypyrazole, polypyrrole, polyaniline, polythiophene or any mixture thereof,
(B) anion-exchange group _-NR ³ + (R = H, alkyl, aryl), pyridinium Pyrr ^+, imidazolium ImR ^+, pyrazolium PyrazR ^+, are those having a triazolium TRIR ^+, or covalently does not form a bridge An anion exchange polymer wherein the polymer backbone is a vinyl polymer, an aryl backbone polymer, polythiazole, polypyrazole, polypyrrole, polyaniline, polythiophene or any mixture thereof,
(C) having both the anion exchange group of (b) and the cation exchange group of (a) on the polymer chain, and the polymer backbone chain is a vinyl polymer, an aryl main chain polymer, polythiazole, polypyrazole, polypyrrole A polymer, which is a polyaniline, polythiophene or any mixture thereof, and (d) a covalent bridge in addition to the ionic bridge, wherein the polymer backbone is a vinyl polymer, an aryl backbone polymer, a polythiazole, A mixture of (a) and (b), which is polypyrazole, polypyrrole, polyaniline, polythiophene or any mixture thereof,
Selected from the group consisting of
The ionomer precursor is
(I) a precursor of a cation exchange polymer,
(Ia) CoHal-, CONR ₂ - or COOR- group (R = H, alkyl, aryl, Hal = F, Cl, Br , I) polymers having,
_{(Ib) SO 2 Hal-, SO} 2 NR 2 - or _SO 2 OR- group (R = H, alkyl, aryl, Hal = F, Cl, Br , I) polymers having,
(Ic) Polymers having PO ₃ Hal ₂ —, PO ₃ (NR ₂ ) ₂ — or PO ₃ (OR) ₂ — groups (R = H, alkyl, aryl, Hal = F, Cl, Br, I) ,
(II) NR ₂ - group (R = H, alkyl, aryl), pyridyl Pyr, imidazolyl Im, pyrazolyl Pyraz, the precursor of the anion-exchange resin containing triazolyl Tri,
Selected from the group consisting of,
Further comprising an ionomer or an ionomer precursor.   The method for producing a composite according to claim 1, wherein the layered or reticulated silicate component is mixed with at least two different base components while the layered or reticulated silicate component is prepared.